Optically sensitized silver halide photographic emulsions

ABSTRACT

WHEREIN Z represents a member from the group consisting of a sulfur atom or a selenium atom; A represents a member from the group consisting of a hydrogen atom, a lower alkyl group or a hydroxyl group; B represents a member from the group consisting of a hydrogen atom or a lower alkyl group; R and R&#39;&#39; represent a member from the group consisting of a lower alkyl group or a substituted alkyl group, and at least one of R and R&#39;&#39; represent a member from the group consisting of a sulfoalkyl group or a carboxyalkyl group; X represents an anion; and n represents 0 or 1, n being 0 when the sensitizing dye is an intramolecular salt. A photographic light-sensitive element comprising the above emulsion on a support is also claimed.   A photographic silver halide emulsion containing a sensitizing dye represented by the formula:

United States Patent [72] Inventors Shiro Klmura;

Yoshiyuki Naliazawa; Yasuharu Nakamura; Akira Sato; Masao Sawahara; Katsuji Yoshida, all of Kanagawa, Japan [21] Appl. No. 842,361 [22] Filed July 16, 1969 [45] Patented Nov. 9, 1971 [73] Assignee Fuji Photo Film Co., Ltd.

Kanagawa, Japan [32] Priority July 16, 1968 1 3 3 1 Japan [31 43/501199 [54] OPTICALLY SENSITIZED SILVER HALIDE PHOTOGRAPHIC EMULSIONS 4 Claims, No Drawings [52] U.S. Cl 96/132, 96/99 [51] Int. Cl G03c l/10H [50] Field of Search 96/ l 06 [56] References Cited 1 v I '7 UNITED STATES PATENTS 3,255,012 6/1966 Glockner et a1. 96/106 3,369,902 2/1968 Abbott 96/106 Primary ExaminerNorman G. Torchin Assistant Examinerlohn L. Goodrow All0rney--Sughrue, Rothwell, Mion, Zinn and Macpeak ABSTRACT: A photographic silver halide emulsion containing a sensitizing dye represented by the formula:

wherein Z represents a member from the group consisting of a sulfur atom or a selenium atom; A represents a member from the group consisting of a hydrogen atom, a lower alkyl group or a hydroxyl group; B represents a member from the group consisting of a hydrogen atom or a lower alkyl group; R and R represent a member from the group consisting of a dye is an intramolecul ar salt.

A photographic light-sensitive element comprising the i above emulsion on a support is also claimed.

BACKGROUND OF THE INVENTION l. Field of the Invention The present invention relates to a silver halide photographic emulsion containing a sensitizing dye, and more particularly to a silver halide photographic emulsion containing a thia-2'- cyanin sensitizing dye or a selena-2-cyanin sensitizing dye which has a hydroxyl group in the 5-position of the benzothiazole nucleus or the benzoselena zole nucleus, and in which a nucleus nitrogen atom in either of the heterocyclic rings is substituted by a sulfoalkyl group or carboxyalkyl group.

2 Description of the Prior Art The spectral sensitizing technique of addingcertain sensitizing dyes to a silver halide emulsion-to further enlarge its light sensitive wavelength range has been well known in the manufacturing technique of silver halide photographic emulsion. Also, the sensitizing dye to be contained in the silver halide photographic emulsion should be such as to provide the desired spectral sensitivity without having a bad influence upon the photographic sensitive materials.

However. a silver halide photographic emulsion which is spectrally sensitized often brings about a color-stain caused by the sensitizing dye after the conventional treatments of development, fixing, washing with water, etc. In black and white photography, the color-stain derived from this dye will act to impede visible judgment ofthe image during printing by virtue of short wavelength lightor platemaking.

Further, there will also occur other problems, as it is unfeasible to obtain a print having an excellent whiteness (one aspect). one cannot obtain the intended color reproduced image in case of color photography. The present invention. as explained hereafter, overcomes these faults.

SUMMARY OF THE INVENTION wherein 2 represents a member from the group consisting ofa sulfur atom or a selenium atom; A represents a member from the group consisting of a hydrogen atom, alower alkyl group or a hydroxyl group; B represents a member from the group consisting ofa hydrogen atom or a lower alkyl group; R andR' represent a member from the group consisting of a lower alkyl group or a substituted alkyl group, and at least one ofR and-R represent a member from the groupconsistingof a sulfoalkyl group or a carboxyalkyl group; X representsan anion; and n represents 0 or I, n being ()when the sensitizing dye is an intramolecular salt.

The above emulsion finds particularuse in a photographic light-sensitive element, wherein the emulsion iscarried on a support.

Therefore. an object of the present invention is to provide a silver halide photographic emulsion having lower color-stain caused by the sensitizing dye, which is produced after carrying out the conventional treatments of development, fixing, washingwith water, etc. Further, the emulsion will have a high sensitivity in the green sensitive range.

Another object of the present invention is to provide a silver halide photographic emulsion having a high sensitivity in the green sensitive range used for a printing or duplication orthofilm, cinema recording film, and indirect photography Roentgen film for medical treatment, etc.

The above objects of the present invention havebeen accomplished by incorporating at least one S-hydroxythia- 2'- cyanin or 5-hydroxyselena- 2'-cyanin sensitizing dyes represented by the fonnula T x-).. r't' (I) wherein Z represents a sulfur atom or a selenium atom; A represents a hydrogen atom, a lower alkyl group, -i.e., one-four carbon atoms, (for example, methyl group. ethyl group, etc.), or a hydroxyl group; B represents a hydrogen atom, or a. lower alkyl group,,i.e., one-four carbon atoms, (for example, methyl group, ethyl group, etc. R and R represent an alkyl group (for example, methyl group, ethyl group, propyl group, etc.) or a substituted alkyl group (for'example.

carboxymethyl group, B-carboxyethyl group, a-carbox'-- .atoms. .However. the sulfosubstituted alkyl group can have from one to six carbon atoms and the carboxy substituted alkyl group can have from one to ID carbon atoms. Further.

acceptable substituents on the alkyl group which may be component R or R are carboxyl groups, hydroxyl groups, alkoxyl groups. a sulfogroup, an aralkyl groupora vinylgroup.

As heretofore indicated. X represents ananiomsuchas a halogen ion (Cl, Br. I), a p-toluene sulfonate ion. -C H O -SO etc.

Thesensitizing dye represented by the-above formula-can be synthesizedby conventional processes, that is. it'can be'obtained by condensing a heterocyclic quaternary ammonium salt represented by the formula: I

R (Ii-1.. (Ill wherein D represents a hydrogen atom. a-loweralkyl group of one-four carbon atoms (for example. methyl ,groupi: ethyl group, etc.), or an alkoxy group of'one-four carbon atoms (for-example, methoxy group, ethoxy group, etc. )1 R, X, and n 1 have the same meaning as-in formula (I); and.R"' representsa methyl group, an ethyl group, or a phenyl .group. etc'.,.and:a*

heterocyclic quaternary ammonium salt represented by the formula hydrobromic acid. Also the sensitizing dye represented by formula (I) can be obtained by the hydrolysis of a sensitizing dye having an alkoxy group in the 5-position of the benzothiazole nucleus, or ofa benzoselenazole nucleus with a mineral acid.

Further, the sensitizing dye of formula (I) used in the present invention as A is a hydroxyl group, may be obtained by the hydrolysis of a sensitizing dye of formula (l) wherein group A is replaced with an alkoxy groupfor wherein group A is replaced with an alkoxy group and the 5-position of the benzothiazole nucleus or the benzoselenazole nucleus has an alkoxy group, with a mineral acid.

Examples. of preparing the sensitizing dye used in the present invention will be described, and further sensitizing dyes used in the present invention will be listed herein. However, the present invention is not limited by these dyes.

lntermediate l 3-ethyl-5-hydroxy-Z-methylbenzothiazolium fonate CH HO p-toluene sullO'g. of 5-hydroxy- Z-methylbenzothiazole and l8 g. of ethyl p-toluene sulfonate were melted by heating at l60 C. and reacted for'4 hours. The resulting crystal, after washing, was

-recrystallized from a mixed solvent of methanol and isopropanol to obtain intermediate (l), melting at l82 C. Yield 19 g.

Intermediate 2) 5 g. of 5-hydroxy-2-methylbenzothiazole and 4 g. of butane sultone were melted by heating at 160 C. and reacted for l hour. The resulting crystal was washed with acetone to provide 6 g. ofintennediate (2) melting at 278 C.

Dye(7) 5 Anhydro l-ethyl-5-hydroxy-6'-methyl-3-(8-sulfobutyl thia-2'-cyanin hydroxide HC s I 10 CH- V-on l CgHs l5 (cmnso;

l.2 g. of l-ethyl-2-ethylmercapto-o-methyl-quinolinium-ptoluene sulfonate and l g. of an'hydro-S-hydroxy-Z-methyl-3- (fi-sulfobutyl) benzothiazoliurn hydroxide were reacted for 2 hours while refluxing at 78 C. in 100 cc. of ethanol and 6 cc.

of triethylamine. The precipitated crystal was separated by filtration and was recrystallized from a solvent mixture of methanol and chlorofonn to obtain l2 g. of dye (7) melting at above 300 C. v

Dye 1 s Anhydro 5,6'-dihydroxy-l '-ethyl-3-(6-sulfopropyl)-thia-2'- cyanin hydroxide Other sensitizing dyes used in the present invention may be prepared in a similar manner to the aforesaid procedure. and typical dyes are illustrated in the following table, together with the above-prepared dyes.

nit-on suitable solvent. such as methanol, ethanol. etc. is added to the emulsion.

The amount of sensitizing dye to be added to the emulsion can be varied over the broad range ofS to I50 mg. per 1 kg. of emulsion. according to the desired final objects.

The photographic emulsion of the presentinvention can be hypersensitized. and supersensitized. in the preparation of the photographic emulsion of the present invention. additives conventionally used. such as, a sensitizer. a stabilizer. a toning agent. a hardening agent. a surface active agent. an antifogging agent. a plasticizer. a developing promotor, a coupier. and a fluorescent whitening agent. may further be added to the emulsion by any conventional method.

The photographic emulsion can be applied to a suitable support. such as a glass, a film of cellulose derivative. a film of synthetic resin. or a baryta paper by any conventional method.

By way of example. the invention will now be defined with greater specificity.

The sensitizing dye of the present invention. as shown above, was added to silver iodobromide emulsion (Agl:AgBr=7 moles: 93 moles) to prepare a photographic emulsion. The emulsion wascoated on a film base of cellulose triacetate and, after drying. exposed to a "day light" of 64 lux (corresponding to 5400 K) through a Fuji No. 17 filter (a green filter, transparent maximum at 525 to 530 u, manufactured by Fuji Photographic Film Co.. Ltd.) and developed.

The developing solution of the composition shown in table 1 was employed at 20 C. for the development temperature.

TABLE I N-methyl-p-aminophenol sulfate 20 g. Hydroquinorie 5,0 g. Cadmium suli'm: I00 g. Borax 2.0 3. Water To l liter Continued MeOl-I. x mt, xmax. A B R R C. mp

CH3 H (CH2)3SO3 (CH2)3SO3HN(C2H5)3 2 7 505 CH3 H C2 5 CH:CH;COO' 118 502 CH: H "C2115 (CH1)3S03' 300 507. 5 CH H -(CH SOr (CH1): :HN(Et)g 2BR 512. 5 CH3 CH3 -C2H5 -(CH2)3SO3 300 50 CH3 H C2H5 CH2COO 259 50-, OH H C2H5 (C2H3 3S03 300 516 on H -cu1. (cHmsor 300 51 The sensitizing dye used in the present invention can spec- TABLE 2 trally sensitize a silver halide photographic emulsion. in par- Mm sensitizing UCUlal'. Is effective for enlarging the spectrally sensitive range 5 lllSlllZlllf! (llllllSlOll Emulsion max. (11m) Sensitivity of gelatino silver halide photographieemulsion, and also can 1 n L Ann. I M560 3'66" satisfactorily sensitize a photographic emulsion containing It 23 71 666-660 4.000 other hydrophilic colloids than gelatin, for example, agar agar. 4 f j I g i 2Z3 g8 water-soluble cellulose derivatives. polyvinyl alcohol. and 2311 550 4.000 other synthetic and natural hydrophilic resins. 25 g? 212% The silver halide to be used in the emulsion of the present TIER-f1 550 3. 640 invention can be various silver salts such as silver chloride. Ag 22; silver bromide, silver iodobromide. silver chlorobromide, and 0.08 2min 55%560 3. 7 0 silver chloroiodobromide. Agltli 292 g??? The sensitized photographic emulsion of the present inven- 2K3) Hi0 2.800 tion may be prepared by adding one or more kinds of sensitiz- 3: 8g g i}: mg dye to the photographic emulsion by the conventional -0 211E761 55x: M 00 7 method. Most practically. a solution of thedye dissolved in a i 570 *Thezvalue of the sensitivity showsthe valu eon exposing a silver iodobrom'ide emulsion to a light thro'ii' h a Fuji No. I?

TABLE 3 AlL'JllOlU/kfl. Density of Sensltizlln: (lyv' emulsion Emulsion Sensitivity color-stain 3, 0. 08 Aullr/l 3. 840 0. 08 10. 0. 0R Aillil'll 3, 500 0. 08 I5. 0. 0X Aglir/l 3. 000- 0. 08 17 0.08 Alc'llt'll 4.800 0.0.| 20 0. 08 Aglir/l 3.100 0.15 21 0.03 AgBr/l 3.100 0. i5 22 0. 0R Agllr/i J, .500 0. i5 23'. 0.08 Aglir/l 2. an 0.15 24 l r 0. 08 Aglir/l 3, 000 0. 20

l Control coloring matter.

The color-stain value shows the density through a Fuji No. 17 filter(transparent maximum 525 to 530 mu. manufactured by Fuji Photographic Film Co.. Ltd.)

CONTROL DYE FORM ULAS CH (control d'yv) -0 n CgHs CgHsSOF CgHs I I I (control dyv) Br On (1H5 Tim (:2) W cm r l r i 1 i \,2.' I (control dye) -0Clla (2115 N As a final point, for instance. in toluene sulfonate ion (CEQSOQ- is bonded with the cation. that is intermediate (l), the p- Accordingly, the bondings" will be clear to one skilled in the art. For instance. in the general (X) n does not represent a floating bond, but generally represents an anion. The anion is bonded with the cation, that is What is claimed is: l. A photographic silver halide emulsion containing a sensitizing dye represented by the formula wherein Z represents a member from the group consisting of a sulfur atom or a selenium atom; A represents a member from the group consisting ofa hydrogen atom, a lower alkyl group or a hydroxyl group; B represents a member from the group consisting of a hydrogen atom or a lower alkyl group; R and R'represent a member from the group consisting of a lower alkyl group or a substituted alkyl group. and at least one of R and Rrepresent a member from the group consisting of a sulfoalkyl group or a carboxyalkyl group; X represents an anion;

andn represents 0 or l, n being 0 when the sensitizing dye is an intramolecular salt.

2. The silver halide photographic emulsion as set forth in claim I, wherein the sensitizing dye is a thia-2'-cyanin compound.

3. The silver halide photographic emulsion as set forth in claim 1, wherein the sensitizing dye is a selena-2'-cyanin compound.

4. A photographic light-sensitive element comprising a support having thereon the photographic silver halide emulsion layer as set forth in claim 1. 

2. The silver halide photographic emulsion as set forth in claim 1, wherein the sensitizing dye is a thia-2''-cyanin compound.
 3. The silver halide photographic emulsion as set forth in claim 1, wherein the sensitizing dye is a selena-2''-cyanin compound.
 4. A photographic light-sensitive element comprising a support having thereon the photographic silver halide emulsion layer as set forth in claim
 1. 